O,o-di(c1 and c2 alkyl)phosphorodithioate and phosphorothioate esters as insecticides and acaricides

ABSTRACT

Disclosed are compounds of the formula:   IN WHICH Y is O or S, each R1 is selected from the group consisting of CH3 or C2H5, and R2, R3 and R4 are H or CH3 with at least one of R2 and R3 being CH3, and the use of these compounds as insecticides and acaricides.

United States Patent Jamison O,O-DI(C AND C, ALKYL) PHOSPHORODITHIOATE AND PHOSPHOROTHIOATE ESTERS AS INSECTICIDES AND ACARICIDES [75] Inventor: Joel D. Jamison, Mountainside, NJ. [73] Assignee: Hercules Incorporated, Wilmington,

Del. 9

[22] Filed: Oct. 27, 1972 [21] Appl. N0.: 301,707

Related U.S. Application Data [60] Division of Ser. No. 136,251, April 21, 1971, Pat. No. 3,741,978, which is a continuationimpart of Ser. No. 694,883, Jan. 2, 1968, abandoned.

[52] U.S. Cl. 424/200, 424/DIG. 8 [51] Int, Cl A0ln 9/36 [58] Field of Search 424/200, DIG. .8; 260/3095 [56] References Cited UNITED STATES PATENTS 2,754,244 7/1956 Gysin et a1. 260/310 R 2,844,582 7/1958 Raley 260/310 R 2,928,841 3/1960 McConnell et a1. 260/3095 2,553,770 5/1951 Kittleson 260/3095 2,886,487 5/1959 Kupferberg et a1 260/3095 2,914,530 11/1959. Schrader et al 260/248 3,111,525 11/1963 Meltzer et a1 260/310 R [4511 May 21, 1974 3,178,447 4/1965 Kohn 260/3095 3,185,699 5/1965 Sherlock 260/309 FOREIGN PATENTS OR APPLICATIONS 728,152 2/1966 Canada 260/310 R 1,093,728 5/1955 France 260/3095 Primary Examiner-Albert T. Meyers Assistant Examiner-Allen J. Robinson Attorney, Agent, or Firm-George H. Hopkins 57 ABSTRACT P. xesemnoun s of h f r u 0 R3-N-("] R1 Y 0-R \e sq R|-C-O/ ILI 0-11 in which Y is O or S, each R is selected from the group consisting of CH, or C H and R R and R" are H or CH with at least one of R and R being CH and the use of these compounds as insecticides and acaricides.

10 Claims, No Drawings st in whichfY is Cor Sfeach R is selected from thegToTp consisting of CH orC H and R, R and R are H or CH with at least one of R and R being CH Specific examples of the compounds are given in the working examples that follow. i a

Most of the compounds of thisinvention are oils at 25C. The others are solid at 2025C. In general I the compounds of this invention are insoluble'in water,

but soluble to the extent sufficient for use as insecticides in solvents such as acetone and the like and in solvents such as benzene and the like. In general the compounds of this'inventio'n are toxic at low concentrations to a number of insects and acarids. Hence, they are useful as insccticidesand acaricides.

. The compounds of this invention are made by one of two processes depicted by the following equations in which l Process No. 2: RECH OQCHt-S-l mamsaaizaa'aaaassaafi tia55555665556? i this invention preferably are incorporated into dispersible compositions which can be solid or liquid.

For insecticidal and acaricidal uses the compounds of this invention preferably are incorporated into dispersible compositions. Such a composition comprises an effective quantity of toxic material and application aid material.

The toxic material consists essentially of at least one compound of this invention. In some embodiments of this composition the toxic material comprises only one compound of this invention. In other embodiments the toxic material comprises two or more compounds of this invention. In still other embodiments, it comprises other substances toxic to one or more insects or acarids, depending on what is desired.

Specific embodiments of the composition of this invention range from concentrates of the toxic material to the ultimate composition that is applied to the habitat of the insects or acarids to be controlled. Accordingly, an effective concentration of the toxic material in the composition of this invention is in a broad range, generally beingfrom about 0.1 to about percent by weight of the composition. Higher and lower concentrations, however, are within the broader scope of this invention. In concentrate embodiments, the concentration of the toxic material generally in a range from about 10 to about 90 percent by weight of the composition and'preferably in a range from about l0 to about 1 50 percent by weight of the composition. In the ultimate use embodiments, the concentration generally is in a range from about 0. 1 toabout 20 percent by weight of the composition and preferably in a range from about 0.5 to about 10 percent by weight of the composition.

Application aid material is generally inert material that facilitates distribution or dispersion of the toxic material when it is applied to the'habitat of the insects or acarids to be controlled. It encompasses diluents, carriers, extenders,surfactants, spreading agents, sticking agents, wind drift control agents, and the like. It also includes inert gas of the kind that is employed in aerosol sprays, when the toxic material is to be applied by aerosol spraying. 1

In those embodiments of the composition of this in vention, which are normally solid, the application aid material generally comprises an inert solid in a divided condition.

Some embodiments of the solid composition are granular, while others are dispersible powders or dusts.

The granular compositions are of the coated type, the impregnated type or the incorporated type.

The coated type of granular composition is made by dusting a wettable powder or ground powder comprising the toxic material onto granular carrier material which either before or after the dusting has been admixed with an adhesive or a sticker. Water, oils, alcohols, glycols, aqueous gums, waxes and the like including mixtures thereof, are used as stickers. Examples of granular carrier material include attaclay, corn cobs, vermiculite, walnut hulls and almost any granular mineral or organic material screened to the desired particle size (generally l5-60 mesh, preferably about 30 mesh, U.S. screen size); Generally the toxic material is about 2-20 percent by weight of the composition, the sticker is generally about 5-40 percent by weight of the com position, and the granular carrier material is generally about 60-93 percent by weight of the composition.

In the case of the impregnated type of granular composition, the toxic material as such when liquid or after melting, or dissolved in a solvent, is sprayed on or poured into the granular carrier material. The solvent can be removed by evaporation, or permitted to remain. In either case, the toxic material impregnates the particles of the granular carrier material. Examples of the granular carrier material include those just mentioned with respect to the coated type of granular composition. The insecticidal material is generally about 2-20 percent by weight of the composition, while the granular carrier material is generally about 80-98 percent by weight of the composition.

The incorporated type of granular composition is made by admixing the toxic material with an inert finely divided solid such as, for example, clay, carbon, plaster of paris and the like, and made into a mud with water or other inert evaporable liquid. The mud is then dried to a solid sheet or cake, broken up or comminuted, and screened to the desired particle size (generally -60 mesh, preferably about 30 mesh, U.S. screen size). in other embodiments, the mud is put into a granular pan and granules are formed therein with subsequent removal of the water or solvent. ln still another procedure, the mud is extruded through a die into rods which are cut into small pieces. In the incorporated type of granular composition, the toxic material generally is about 2-50 percent by weight of the composition, and the solid carrier material is about 50-98 percent by weight of the composition.

in all granular embodiments of the composition of this invention, various additives in minor concentrations relative to the carrier material also can be present.

in other embodiments of the solid composition of this invention, the carrier is usually a dispersible inert solid. A typical dispersible solid of this type is clay; Other suitable solids (dispersible solid) include talc, attapulgite, pyropylite, diatomaceous earth, kaolin, aluminum magnesium silicate, montmorillonite, fullers earth, sawdust and the like. The solid dispersible composition can be air dispersible, in which case it is usually referred to as a dust. Generally, when it is intended that the composition be water dispersible, the composition preferably contains emulsifying material (one or more surfactants) at a concentration sufficient to enable a suspension of the desired degree of stability to be formed when the composition is admixed with a suitable quantity of water. The composition in such case is usually referred to as a wettable powder. A typical dispersible solid composition of this invention generally comprises about 10-50 percent by weight of toxic material, about 50-90 percent by weight of solid carrier material and, when emulsifying material is present, about i-lO percent by weight of emulsifying material.

Other specific embodiments of the toxic composition of this invention comprise homogeneous liquid solutions of toxic material in inert, preferably volatile, usually water immiscible solvents for the toxic material. Examples of suitable solvents include isophorone, cyclohexanone, methyl isobutyl ketone, acetone, xylene, benzene, toluene, and the like. Such a solution, which can be regarded as a concentrate, typically comprises about 10-50 percent by weight of toxic material and about 50-90 percent by weight of solvent. The solution can be applied as is, or diluted with more solvent, or dispersed in water, or water dispersed in it. Preferably, when it is intended that the solution be dispersed in water or water dispersed in it, the mixture of solution and water also comprises emulsifying material at a concentration sufficient to enable a dispersion of the desired degree of stability to be formed when the solution or concentrate is mixed with water. A typical emulsifying material concentration is about l-l0 percent by weight of the concentrate. The water concentration generally is such that the toxic material concentration preferably is about 05-10 percent by weight of the total composition.

Examples of the surfactants employed in both the liquid and solid compositions of this invention comprise the well-known surface active agents of the anionic, cationic and non-ionic types and include alkali metal (sodium or potassium) oleates and similar soaps, amine salts of long chain fatty acids (oleates), sulfonates, ani mal and vegetable oils (fish oils and castor oil), sulfonated acyclic hydrocarbons, sodium salts of lignin sulfonic acids, alkylnaphthalene sodium sulfonates, so dium lauryl sulfonate, disodium monolauryl phosphate,

sorbitol laurate, pentaerythritol monostearate, glycerol monostearate, polyoxyethylene, ethylene oxide condensates of stearic acid, stearyl alcohol, stearyl amine, rosin amines, dehydroabietyl amine and the like, lauryl amine salts, dehydroabietyl amine salts, lauryl pyridium bromide, stearyl trimethylammonium bromide, and cetyl dimethylbenzylammonium chloride. Still other examples are listed in Detergents and Emulsifiers l968 Annual by John W. McCutchen.

in addition to the. toxic material and application aid material, some specific embodiments of the insecticidal composition of this invention comprise one or more other components, examples of which include other insecticides and acaricides, insect and acarid attractants, herbicides, fungicides, plant nutrients, and the like.

The dispersible composition of this invention is used by applying it by conventional ways and means to the habitat of the insect or acarid to be controlled. When it is desired to take advantage of the systemic toxicity of a systemically active compound of this invention, the composition is applied as by spraying to the seeds of plants on which the systemically affected insects feed prior to planting, by laying or drilling the composition in granular form next to or with the seeds being planted, or spraying or dusting the leaves of the growing plants in the early stages of their growth.

The rateof application of the dispersible composition of this invention is such as to provide an effective concentration of the toxic material in the habitat of the insect or acarid to be controlled. Such a concentration depends on the toxic material and on the insect or acarid to be controlled.

The best mode now contemplated of carrying out this invention is illustrated by the following working examples of various aspects of this invention, including specific embodiments. This invention is not limited to these specific embodiments. ln the examples all percentages are by weight unless otherwise indicated.

EXAMPLE 1 This example illustrates how to make 0,0-dimethyl S-( l-methyl-2,4-imidazolidinedione-3-yl)methyl phosphorodithioate.

A mixture of 285 g. of. l-methyl-2,4- imidazolidinedione, 80 g. of paraformaldehyde and 1.0 g. of barium hydroxide is melted and heated at 90C. for 1 hour. The melt is taken into 1,200 ml. methylene chloride and treated with 550 g. (2.64 m.) of phosphorouspentachloride at C. After 18 hours at room temperature, the solvent is removed and the crude mixture distilled to give 301.4 g. of an intermediate product consisting essentially of 3-chloromethyl-l-methyl-2,4- imidazolidinedione (b.p. l55C./4.0 mm.; found: Cl 21.7%, calculated: CI 21.8%).

A mixture of 9.8 g. of 3-chloromethyl-l-methyl-2,4- imidazolidinedionc and 11.0 g. of ammonium 0,0- dimcthyl phosphorodithioate in 50 ml/acctonitrileis stirred for 10 hours at 25C., and then for 3 hours at 60C. The mixture is then poured into 200 ml. water. The organic layer is taken up in 100 ml. benzene, and the benzene solution is washed with 5 percent aqueous sodium bicarbonate solution and then with water, and dried. Distilling off the benzene gives 16.1 g. ofa colorless oil consisting essentially'of 0,0-dimethyl S-(lmethyl-2.44midazolidinedione-3-yl) methyl phosphorodithioate. A typical element analysis of the oil is P 11.0%; calculated: P 10.9%.

EXAMPLE 2 This example illustrates how to make 0,0-diethyl S- l-methyl-2,4-imidazolidinedione3-yl)methyl phosphorodithioate.

8.7 g. of 3-chloromethyl-l-methyl-2,4- imidazolidinedione made as in Example 1 and 14.0 g. of ammonium 0,0-diethyl phosphorodithioate are reacted by the procedure and under the conditions of the second paragraph of Example 1.

The product (11.7 g.) typically is a dark oil which analysis P 10.0% (Calculated: P 9.9%). It consists essentially of Q,O-diethyl S-( l-methyl-2,4- imidazolidinedione-S-yl)methyl phosphorodithioate.

EXAMPLE 3 This example illustrates how to make 0,0-dimethyl S-[ l-( l '-methyl-2',4'-imidazolidinedione-3-yl)ethyl] phosphorodithioate.

A mixture of 57 g. of l-methyl-2,4- imidazolidinedione. 46.2 g. of ethylene carbonate and 0.3 g. sodium bicarbonate is heated to l50200C. until CO evolution ceases. The product mixture is cooled, diluted with 300 ml. of pyridine and treated with 60 g. of acetic anhydride. After heating this mixture at C. for 4 hours, it is stripped of solvent, and the crude product is distilled to give 88.2 g. of purified first intermediate product (b.p., l30-l36C./0.2 mm.; elemental analysis Found: N 13.9%, calculated N 14.0%) which consists essentially of l-methyl-3-(2'- acetoxyethyl)-2,4-imidazolidinedione.

Purified first intermediate product (60 g.) is added at 0.5 ml./minute to a 12 X 1 inch packed tube at 550C. The crude pyrolysate is distilled to give 18 g. of second intermediate product (b.p. 8689C./0.3 mm.) consisting essentially of 'l-methyl-3-vinyl-2,4- imidazolidinedione.

To a solution of 7.6 g. second intermediate product in 10 ml. benzene is added dropwise 10.3 g. 0.0- dimethyl phosphorodithioieacid at 25C. An exothermic reaction occurs. The reaction mixture is permitted to stand at 25C. for about 18 hours. The resulting solution is diluted with 50 ml. benzene, washed with two 50 ml. portions of 5 percent aqueous sodium bicarbonate solution and then with water, and dried. The benzene is distilled off, leaving 15.7 g. of a clear oil consisting essentially of 0,0-dimethyl S-[ l-( l -methyl-2,4'- imidazolidinedione-3yl)ethyl] phosphorodithioate. A typical elemental analysis of the oil is: P =.10.9%; cal culated: P 10.4%.

EXAMPLE 4 This example illustrates how to make 0,0-diethyl S [1-( l '-methyl-2',4-imidazolidinedione-3'-yl)ethyl] phosphorodithioate.

A solution of 22.3 g. of QO-diethyl phosphorodithioic acid in 10 ml. of benzene is added to a solution of 14.0 g. of 1methy1-3-vinyl-2,4-imidazolidinedione (made as in Example 3) in 50 ml. of benzene without any indication. of an exothermic reaction. The resulting solution is refluxed for 6 hours, cooled, washed with two 50 ml. portions of 5 percent aqueous sodium bicarbonate solution, two 50 ml. portions of water, and dried. The benzene is removed by distillation, leaving a yellow oil consisting essentially of 0,0-diethyl S-[ ll -methyl-2,4-imidazolidinedione-3-yl)ethyl] phosphorodithioate. A typical elemental analysis of the oil is: P 9.9%; calculated: P 9.5%.

EXAMPLE 5 This example illustrates how to make 0,0-diethyl S- l-methyl-2,4-imidazolidinedione-Il -yl)methyl phosphorothioate.

To a solution of 20.6 g. ammonium 0,0-diethyl phosphorodithioate in 100 ml. dimethylsulfoxide at 25C. is gradually added 16.2 g. 3-chloromethyl-1methyl-2,4- imidazolidinedione (made as in Example 1 A mild exothermic reaction typically results, raising the temperature to 37C. After storing the reaction mixture at am bient temperature for 18 hours, the resulting solution is heated at 60C. for 3 hours, and then cooled. The product is worked up by diluting with 1,000 ml. water and extracting with methylene chloride. The organic layer is washed with water and dried, and the desired product is recovered by distilling off the methylene chloride. The product (25.5 g.) is typically a yellow oil analyzing P 10.4%; calculated: P 10.5%. lt consists essentially of 0,0-diethyl S-( l-methyl-2,4- imidazolidinedione-B-yl )methyl phosphorothioate.

EXAMPLE 6 In this example 0,0-dimethyl S-(1-methyl-2,4- imidazolidinedione-3-yl)methyl phosphorothioate is made.

A mixture of 3-chloromethyl-l-methyl-2,4- imidazolidinedione (51.2 g.), made as in Example 1, and ammonium 0,0-dimethyl phosphorothioate (53 g.) in 200 ml. of acetonitrile is stirred at 25C. for 48 hours and at 60C. for 3 hours. The mixture is filtered, the acetonitrile is removed, and the residue is taken up into 800 m1. of methylene chloride. The methylene chloride solution is filtered and the solvent removed to give 80.8 g. of the desired product, typically an amber oil analyzing: P 11.8%, N 10.2% (calculated: P 11.6%, N 10.4%). The product consists essentially of 0,0 dim ethyl S- (1-methyl-2,4-imidazolidinedione; 3-yl) methyl phosphorothioate.

EXAMPLE 7 This example pertains to 0,0-dimethyl S-(1,5- dimethyl-2,4-imidazolidinedione-3-yl)methyl phosphorodithioate.

1,5-climethy1-3-chloromethyl-2,4-imidazolidinedione is made in the same way as 3-chloromethyl-l-methyl- 2,4-imidazolidinedione is in Example 1, using 1,5- dimethyl-2,4-imidazolidinedione in place of l-methyl- 2,4-imidazolidinedione. The product distills at l09C./ 2.0 mm.

A mixture of 11.6 g. 1,5-dimethyl-3-ch1oromethyl- 2,4-imidazolidinedione and 11.5 g. ammonium 0,0- dimethyl phosphorodithioate in 100 ml. acetonitrile is heated at 60C. for 8 hours. The acetonitrile is distilled off, and the residue is diluted with 100 ml. ether, washed with percent aqueous sodium bicarbonate solution and then with water, and dried. On distilling off the ether, there is obtained 1 1.0 g. of the desired product which consists essentially of 0,0-dimethyl S-(1,5- dimethyl-2,4-imidazolidinedione 3-yl) methyl phosphorodithioate. The product typically analyzes P 11.9%; (Calculated: P 10.4%).

EXAMPLE 8 This example is concerned with 0,0-dimethyl S-[ 1- (2,4-imidazolidinedione-3-yl)ethyl] phosphorodithioate.

3-Vinyl-2,4-imidazolidinedione is made in the same way as l-methyl-3-vinyl-2,4-imidazolidinedione is in Example 3, using 2,4-imidazolidinedione in place of lmethyl-2,4-imidazolidinedione. The product distills at 155C./l.0 mm. and melts at 8789C. after recrystallization from isopropanol.

A mixture of 2.3 g. 3-vinyl-2,4-imidazolidinedione and 5 ml. 0,0-dimethyl phosphorodithioic acid is heated cautiously and gradually to 95C. with precautions for cooling to control the exothermic reaction. The reaction mixture thus formed is maintained for 3 hours at 8090C. The reaction mixture is cooled, diluted with 40 ml. benzene, washed with 5 percent aqueous sodium bicarbonate and water, and then dried. The benzene is distilled off to give 5.6 g. solid product consisting essentially of 0,0-dimethyl S-[ l-(2',4'- imidazolidinedione-3-yl)ethyl] phosphorodithioate. This product after recrystallization from isopropyl alcohol typically melts at 1 l0-l 12C., and analyzes P 10.9%;(Calculated: P 10.9%).

EXAMPLE 9 EXAMPLE 10 This example illustrates an emulsifiable concentrate of this invention and how to make it.

The formulation of this concentrate is as follows:

Components Quantities Toxic material 1 part by weight Polyoxyethylene (20) sorbitan monolaurate 1 part by volume Toluene 1 part by volume Each part by weight bears the same relationship to each part by volume as the kilogram to the liter. The toxic material consists essentially of one or more of the products of Examples l-9.

The emulsifiable concentrate of the above formulation is made by admixing the components at 20-25C.

The emulsifiable concentrate is used by admixing it with sufficient water to give an oil-in-water emulsion in which the concentration of the toxic material is about 1 percent by weight of the emulsion.

The emulsion is used by spraying it over the habitat of the insects or acarids to be controlled.

Typical results obtained in the insecticidal and acaricidal testing of the products of Examples 1-9 are presented in Table 11. The procedure followed to obtain these data is as follows:

An emulsifiable concentrate ,of the product and having the formulation of Example 11 is made and admixed with enough water to give an oil-in-water emulsion in which the toxic material concentration is 1.0 percent by weight of the emulsion. For lower concentrations, portions of the emulsion were admixed with the quantities of distilled water needed to give the desired concentration.

In a number of instances, if a sample of the product at the initial test concentration resulted in a percent kill of a particular insect or acarid, it was tested at lower concentrations relative to that insect or acarid.

Exemplary of the test procedures are the contact toxicity tests on the Mexican bean beetle, pea aphid and two-spotted mite and the systemic toxicity tests on the two-spotted mite and pea aphid, which are described as follows:

Contact Toxicity Test Mexican Bean Beetle Mexican Bean Beetle: A freshly cut 7 centimeter leaf of a lima bean plant is supported by its stem placed in 55 0 220 m m io z n8 8 8 88 88 H8 82 28 8 8 28w H 88 88 82 88 88 8w 88 82 88 88 E 0 w o z swo 88H 882 8 8 H \8H 88 8 82 H \8H H \8H H \8H H \82 8 2. U H MILNO m 0 0 w mo Z l l I h E O m Z EO 2\82 8 8 H8 \8H 8 \8H 88 8\8H 8 8 H 82 888 H 8H H 88 H 8 88 \8H 88 \8H 8 8 o H mo o o mo m m Wu Z 8 m Eo o m 50 o Z Eo n82 H 88 82 H8 8 88 \8 828m 88H 8 8w 88 28H 282 832 H \8H 8H8w 8 \8H H8 \8H 2 8 8 \8H 88 \8H 8 \8H o H Ho e o mo m w mo z h 82 82 HH O O m OIZLMO 28m 282 88 \8 88 \8H 88 \8H 88 8 -N S\8H 882 8 88 H8 8 88 8 8 8 \8H 8 8 m8 \8H 882 8 8m 0 8 "mo e o mo fiH m mo z k H888 mo e w o z mo 28H 282 88 1 88 2. 88 8 88 82 88 \8H 88 88 882 882 8 \8H 8H 88 H8 H8 \8H 8 88 m8 \8H 88 82 8 5. o m 252. m 82o .522 3: om 25m. 84m 4m MES 2m 2 28 8 8 2 8 $2 m m I E 250 5 280 un wmmom w .522 5 ASE 2mm. 8 llallllllil 8 82 EH2 H 2 0 BE 3 3$ 52 8 E38 88 0 M 58 03w Eo H m 3 28 2 2 HH w qfimw 38H H x m e zwa 28 6=-$HE2W 88%25423 25mH m 2 2$ 33 gs w k mws E H H m fiw 2 3 8 22 4 m mqm 28 m 3 u mm oflDoHDU EUFHHOAH MPH wmdam flm m%vm 55 0 0 50 m w m z m6 o m EM Z w 822 I} Q? s \2 2 .18 $82 382 8 3 2 8 823 2 8 :8 :8 8 82 2 S2 8 \E o 8 mo 0 nw mo m m m z b w .51. w .5 8 2 8o .2 wfififi K 8 82 :6 8282 8 82 Q3 :8 88 82 8 2 8 82 o w 8 "mo e o mo mo m m mo z \P mo e m o z mo 5 3 8 2 28x8 838 838 882 882 8 8 82 828 2 8 2 82 2 3 8Q SH 3 o 1 b mo o o mu .m m E0 z :12 \h 28 3 88 82 88 88 ....-..........-.1...-.8&3 0 w m 2B2 2B2 1 8 8 8282 :12 8 82 28 82 28 82 823m 3B2 852 8 3 :82 823 88 82 88 82 :02 8:2 88 82 8 82 o w W W22. 9B 220 .2 3: 0m 22. 84m 3 mm; mm 22 8 35 5 0 2 .8 32 E I m dfimb 5 250 5323M 5 5 E; 58 58 hav 2 2% a n w w E3 0 a cotton-stoppered 3.5 milliliter water-filled vial, and I the leaf is sprayed with emulsion and allowed to dry. The leaf in its vial is placed in a plastic sandwich box 1 1 X l3 X 4 centimeters'with l Mexican bean beetle larvae (2nd to 3rd instar) and held at 78F. and 50 percent relative humidity for 48 hours. The mortality is then observed. Contact Toxicity Test Pea Aphid Ten adult pea aphids are placed in the cover of a cylindrical screen cage and sprayed with emulsion. The aphids are then placed on a pea plant in the cylindrical cage, the cover put in place, and the caged aphids held for 24 hours at 6065F. and 50 percent relative humidity. The percent mortality is then determined. Contact Toxicity Test Two-Spotted Mite Lima bean seedlings 5-6 days old are infested with 50 phosphate-resistant two-spotted mites at various growth stages, and the emulsion is sprayed on both sides of the leaves of the infested plants to run-off. The seedling stems are placed in fresh water, and held at 78F. at 50 percent relative humidity for 6 days. The

mortality is then determined.

Systemic Toxicity Test Two-Spotted Mite A rooted lima bean seedling (5-6 days old) which has been grown under test conditions is placed in a culture tube containing emulsion. Fifty to 100 Two-Spotted Mites which are not phosphate resistant are placed on the leaves of the seedling immediately. The seedling is then stored at 78F. and 50 percent relative humidity for 6 days. The-kill is then determined. Systemic Toxicity Test Pea Aphid A rooted lima bean seedling (5-6 days old) which has been grown under test conditions is placed in a culture tube containing emulsion. Twenty-four hours later 10 adult pea aphids are placed on the leaves of the seed ling. The seedling is then held at 6065F. and 50 percent relative humidity for 2 days. The mortality is then observed.

temic toxicities at practical concentrations to insects and acarids. Hence, this invention provides new and useful insecticides and acaricides.

These and other features, advantages and specific embodiments of this invention will become readily apparent to those exercising ordinary skill in the art after reading-the foregoing disclosures. Such specific embodiments are within the scope of the claimed subject matter unless expressly indicated to the contrary by claim language. Moreover, while specific embodiments of this invention have been described in considerable detail, variations and modifications of them can be effectedwithout departing from the spirit and scope of the invention as disclosed and claimed.

The term consisting essentially of as used in this specification excludes any unrecited substance at a concentratiqn .ssfisisnt t j sbsts ia ly as vsrsslxafi From these aera iressb seenthat the co m p ounds I of this invention as a group have both contact and syst 40 feet the essential properties and characteristics of the composition being defined, while permitting the presence of one or more unrecited substances at concentrations insufficient to substantially adversely affect said essential properties and characteristics.

What I claim and desire to protect by Letters Patent is:

1. An insecticidal and acaricidal composition comprising an inert carrier and an insecticidally and acaris al y. sffsstixssmqvn o sm osad q t qtm l in which Y is selected from the group consisting of O and S, each R is selected from the group consisting of ,CH;, and C H and R, R and R are selected from the group consisting of H and CH with at least one of R and R being CH 2. The composition of claim 1 in which each R is CH R is H, R is CH R is H, and Y is S.

3. The composition of claim 1 in which each R is CH R is H, R is CH R is H, and Y is O.

4. The composition of claim 1 in which each R is 6 CH R is CH5, R is CH;,, R is H, and Y is S.

I 5. The composition of claim 1 in which each R is lC l-l R is H, R is CH;,, R is H, and Y is S.

6. A method for controlling insects and acarids, which comprises applying'to the habitat of said insects !and acarids an insecticidally and acaricidally effective amount of a compound of the formula: H

in which Y is selected from the group consisting of O and S, each R is selected from the group consisting of CH, and C H and R R and R are selected from the group consisting of H and CH with at least one of R and R being CH 7. The method of claim 6 in which each R is CH R is H, R is CH R is H, and Y is 8. The method of claim 6 in which each R is CH R is H, R is CH R is H, and Y is O.

9. The method of claim 6 in which each R is CH R is CH R is CH;,, R is H, and Y is S.

10. The method of claim 6 in which each R is C H R is H, R is CH,,, R is H, and Y is S.

izg gg V UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,812,253 Dated May 21, 1974 Ihventofls) Joel D. Jamison (Case-6-l4-l7) hove-identified patent It is certified that er ror appears in the a d as shown below:

and that said Letters Patent are hereby correcte Column 1, second half section of last formula:

g "f/O-R should be '1 O-1-cH-s-P 1 C V C H:-5* 1 l o- (J-R Columfi 11, Product of Ex. 6, s tructural formula;

0, ou -u---c ,0-cH should be 3? N43 39 9 3 1 /N-CH2'QS?P\ H CH (3 2 o cfi 7 Signed and sealed this 4th day of February 1975.

(SEAL) Attest:

Mc COY M. GIBSON JR. Attesting Officer C. MARSHALL DANN Commissioner of Patents 

2. The composition of claim 1 in which each R1 is CH3, R2 is H, R3 is CH3, R4 is H, and Y is S.
 3. The composition of claim 1 in which each R1 is CH3, R2 is H, R3 is CH3, R4 is H, and Y is O.
 4. The composition of claim 1 in which each R1 is CH3, R2 is CH3, R3 is CH3, R4 is H, and Y is S.
 5. The composition of claim 1 in which each R1 is C2H5, R2 is H, R3 is CH3, R4 is H, and Y is S.
 6. A method for controlling insects and acarids, which comprises applying to the habitat of said insects and acarids an insecticidally and acaricidally effective amount of a compound of the formula:
 7. The method of claim 6 in which each R1 iS CH3, R2 is H, R3 is CH3, R4 is H, and Y is S.
 8. The method of claim 6 in which each R1 is CH3, R2 is H, R3 is CH3, R4 is H, and Y is O.
 9. The method of claim 6 in which each R1 is CH3, R2 is CH3, R3 is CH3, R4 is H, and Y is S.
 10. The method of claim 6 in which each R1 is C2H5, R2 is H, R3 is CH3, R4 is H, and Y is S. 